Azo compounds and material colored therewith



Patented Nov. 4, 1941 Azo COMPOUNDS AND'MATERIAL COLORED THEREWITH JamesG. McNally and Joseph B. Dickey, Roches- .ter, N. Y., assignors toEastman Kodak Company, Rochester, N. Y., a corporation of New Jersey NoDrawing. Application July 1, 1939,

, 1 Serial No. 282,527

8 Claims. (Cl. 260-155) vThis invention relates to the art of dyeing orcoloring. More particularly, it relates :to arylazo dye compounds andthe application of the nuclear non-sulfonated arylazo dye compounds forthe coloration of organic derivativesof cellulose, particularly textilematerials made of or containing an organic derivative of cellulose bydyeing, printing, stenciling or like methods.

Organic derivatives of cellulose are characterized by an indifferentafiinity for the usual cotton and wool dyes especially the ordinarywater soluble dyes. Because of this, it has been necessary to developnew dye compounds suitable for the dyeing or coloration of materials,such as textile materials, made 'of or containing an organic derivativeof cellulose. It is, accordingly, an objectof our invention to provide anew class of azo dyes suitable for the dyeing or coloration of organicderivatives of cellulose. Another object is to provide a process for thecoloration of organic derivatives of cellulose in which the dye or dyesare applied directly from an aqueous suspension to the materialundergoing coloration. A further object is to produce dyeings on organicderivatives of cellulose which are of good fastness to light andwashing. Other objects will hereinafter appear. I

Typical organic derivatives of cellulose include the hydrolyzed as wellas the unhydrolyzed cellulose organic acid esters such as celluloseacetate, cellulose formate, cellulose propionate, or cellulose butyrateand the hydrolyzed as well as the unhydrolyzed mixed organicacid estersof cellulose such as cellulose acetate-propionate, celluloseacetate-butyrate, and the cellulose ethers such as methyl cellulose,ethyl cellulose, or benzyl cellulose. While our invention will beillustrated more particularly in' connection with the coloration ofcellulose acetate, a material-to which the invention is especiallyadapted, it will be understood that it applies to the coloration ofother organic derivatives of cellulose suchas those just mentioned.

The arylazo dye compounds of our invention have the general formula:

wherein R represents the residue of a member selected from the groupconsisting of a benzene nucleus, a naphthalene nucleus and an azobenzenenucleus, B represents the residue of a benzene nucleus, R1 represents amember selected from the group consisting of hydrogen and an alkylgroup, R2 and R3 each represents a member selected from the groupconsisting of hydrogen, an alkyl group and an amino group, wherein eachof the hydrogen atoms shown attached to the carbon atoms numbered 2, 3and 4 can be replaced by an alkyl group and wherein the nitrogen atomnumbered 1 and the carbon atom numbered l are joined to said benzenenucleus'B in para and meta position, respectively, to the azo groupshown. Advantageously, R is the residue of a benzene nucleus. 7

It will be understood that alkyl, as herein,

ples which follow hereinafter. These nuclei can be substituted, forexample, with a substituent such as a nitro group, a halogen atom, .analkyl group, a hydroxy group, or an alkoxy group. Illustrative ofhalogen may be. mentioned chlorine, bromine and iodine. Similarly,illustrative of alkoxy may be mentioned 'methoxy, ethoxy, propoxy,butoXy, fi-methoxyethoxy and fi-ethoxyethoxy.

The azo dye compounds of our invention can be prepared by diazotizingayprimaryarylamine and coupling the diazonium compound obtained with acoupling componenthaving the general formula:

wherein B represents the. residue of a benzene nucleus, R1 representshydrogen or .an alkyl group, R2 and R3 each represents hydrogen, an

alkyl group or an aminovv group and wherein each.

of the'h'ydrogen atoms shown attached to the carbon atoms'numbered 2, 3and 4 can be replaced by an alkyl group; 1.

As previously indicated, the nuclear non-sub fonated arylazo dyecompounds of our invention constitute valuable dyes for the colorationof organic derivatives of cellulose, such as those hereinbeforementioned, yielding various shades thereon of good fastness to light andwashing. These nuclear non-sulfonated dye compounds likewise possesssome application for the dyeing of wool and silk and yield generallysimilar shades on these materials as on organic derivatives ofcellulose.

Azo compounds having the above general formula containing a nuclearsulfonic acid group can likewise be prepared in known fashion. Suchcompounds may be prepared by sulfonation of the unsulfonated azo dyecompounds or by prior sulfonation of the intermediates employed. Thesenuclear sulfonated compounds possess little or no utility for thecoloration of organic derivatives of cellulose but can be employed tocolor textile materials such as wool and silk yielding generally similarshades as the corresponding non-sulfonated compounds. Accordingly, whenthe azo compounds of our invention are employed for the dyeing oforganic derivatives of cellulose, they should not contain a nuclearsulfonic acid group. Again, it is generally advantageous when they areto be used for this purpose that they do not contain a free nuclearcarboxylic acid group. I

We are aware that U. S. Patent No. 2,067,726, issued January 12, 1937,describes the preparation of azo dyes obtained by diazotizing anitroaminobenzene and coupling the diazo compound obtained with a12,3,4-tetrahydrcquinoline of the general formula:

lliydrocarbon radicle ER 8 7 2(EH2 c 3on0 wherein X means hydrogen oralkyl and in which the benzene nucleus may be substituted by alkyl,halogen or alkoxy. These water-insoluble dyes, free from sulfonicandcarboxylic acid groups, are stated to be particularly advantageous fordyeing cellulose esters, especially acetate silk. No claim is made tothese dyes.

The azo dye compounds of our invention differ chemically from those justdescribed in that the tetrahydroquinoline coupling component contains nohydroxyl or alkoxy group in the 3- position. Again, generally speaking,the azo dye compounds of our invention possess the advantage of beingmore readily and economically prepared than those of the characterdisclosed in Patent No. 2,067,726. In this connection, it will be notedthat this patent contains no description of the preparation of the1,2,3,4-tetrahydroquinoline compounds. However, British Patent No.458,423, corresponding thereto, states that they can be obtained bycondensation of the appropriate alkylor aralkylamino benzenes withepichlorhydrin at a raised temperature whereby ring closure occurs withthe formation of the tetrahydroquinoline derivative (see page 1, lines34-41) We have tried several times to prepare these compounds followingthe directions given for their preparation but have had poor success.

In contrast thereto the new tetrah'ydroquinoline coupling components ofour invention, depending upon their particular structure, can be readilyprepared by varying methods which differ from that of British Patent No.458,423. Tetrahydroquinoline compounds of our invention can be preparedby hydrogenating quinoline or suitable quinoline derivatives in thepresence of a catalyst such as Raney nickel. Substituted quinolines canbe prepared from the corresponding substituted aniline compounds usingthe Skraup synthesis. 7-methylquinoline, for example, can be preparedfrom meta-toluidine using this method. Compounds such as2,2,4-trimethyltetrahydroquinoline are prepared by reacting aniline orsubstituted anilines with a ketone such as acetone methylethyl ketone,diethylketone etc., together with a suitable catalyst or catalysts asdescribed in Berichte, vol. 65, page 1511 (1932); Journal AmericanChemical Society, vol. 55, page 2805 (1933); Berichte, vol.

' 54, page 1723 (1921) and hydrogenating the dihydro alkyl substitutedquinolines thus formed.

The dye compounds of our invention. in general, yield dyeings on organicderivatives of cellulose, especially cellulose acetate silk, of goodfastness to light and washing. Further, the dye compounds of ourinvention possess good aflinity for cellulose acetate silk fibers anddye this material rapidly at temperatures as low as -65 C. This propertyof rapid dyeing at low temperatures is of advantage in that iteliminates the necessity of dyeing at higher temperatures and therebylessens the danger of damaging the fiber.

Again, as is well known in the art, there has been di'fiiculty insecuring dischargeable blue dyes for cellulose acetate. In addition tothe difficulty of obtaining a dischargeable blue dye, there is thefurther difficulty of obtaining one which is both stable to light andresistant to acid fadme. We have discovered that certain of the dyecompounds of our invention yield blue dyeings on cellulose acetate silkwhich are dischargeable, fast to light and very resistant to acidfading. The dyes having these properties can, for the most part, berepresented by the general formula:

onzononcmon 7 NO. N N ,Q

2CH2 Y z 4 3/ HzC-OH:

wherein X represents a member selected from the group consisting ofhydrogen, chlorine and bromine, Y represents a member selected from thegroup consisting of hydrogen and a nitro group, and Z represents amember selected from the group consisting of hydrogen and methyl, saidcompounds being further characterized in that X and Y cannot both behydrogen at the same time. Special claim is laid to these dyes becauseof their unusually excellent properties which could not be foreseen.

The following examples illustrate the preparation of the azo dyecompounds of our invention:

Example 1 13.5 grams of p-aminoacetophenone are dissolved in 200 cc. ofwater containing 25 cc. of 36% hydrochloric acid. The resulting solutionis cooled to a temperature approximating 05 C. and the amine isdiazotized at this temperature by adding with stirring a water solutionof 6.9 grams of sodium nitrite.

13.3 grams of tetrahydroquinoline are dissolved in cc. of watercontaining 10 cc. of 36% hy-.

drochloric :acid. The resulting solution is cooled to 'a temperatureapproximating -10 C. and the diazo solution preparedas described aboveis added with stirring. The coupling reaction which takes place iscompleted by adding sodium acetate. The dye compound formed is recoveredby filtration, washed with water and dried. This dye compound colorscellulose acetate silk an orange shade.

Example 2 17.3 grams of 1-amino-2-chlorol-nitrobenzene are diazotized inknown fashion and the diazonium compound obtained is coupled in a coldaqueous hydrochloric acid solution with 17.7 grams of 18-hydroxyethyltetrahydroquinoline. Coupling and recovery of the dyecompound may be carried out as described in Example 1. The

dye compound obtained colors cellulose acetate silk a rubine shade.

Example 3 18.3 grams of 1-amir1o-2,4-dinitrobenzene are diazotized andthe diazonium compound obtained is coupled with 20.5 grams ofl-glyceryltetrahydroquinoline. Coupling and recovery of the dye compoundmay be carried out as described in Example 1. lulose acetate silk aviolet shade.

Example 4 21.8 grams of 1-amino-2,4-dinitro-6-chlorobenzene arediazotized and the diazonium compound obtained is coupled with 21 gramsof l-glyceryl-lmethyltetrahydroquinoline. The dye compound obtainedcolors cellulose acetate silk a blue shade.

Example 5 26.3 grams of 1-amino-2,4-dinitro-G-bromobenzene arediazotized and the diazonium compound obtained is coupled with 24 gramsof l-fi-hydroxy 'ychloropropyl-T-methyltetrahydroquinoline. Coupling andrecovery of the dye com pound may be carried out as described inExample 1. The dye compound obtained colors cellulose acetate silk ablue shade.

Example 6 30.9 grams of 1-amino2,4 dinitro-6-fluorobenzene arediazotized and the diazonium compound obtained is coupled with 31.2grams of The dye compound obtained colors cellulose acetate silk a blueshade.

Example 7 25.2 grams of 1amino-2,4=-dinitro-3,6-dichlorobenzene arediazotized and the diazonium compound obtained is coupled with 19.1grams of l- -hydroxypropyl-5-methyltetrahydroquinoline. The dye compoundobtained colors cellulose acetate silk a blue shade.

Example 8 7.2 grams of sodium nitrite are dissolved in 50 cc. of warmsulfuric acid (100%) following which the solution resulting is cooled toroom temperature.

The dye compound obtained colors cel-,

1 tetrahydroquinoline.

22.8 grams of picramide are pulverized and added to the solutionprepared above and the mixture resulting is stirred for 40 hours at35-40 C. 27 grams of are dissolved in sulfuric acid at 0-10 C. and thediazo solution prepared above is slowly added with stirring. Thecoupling reaction which takes place is carried out while maintaining atemperature approximating 0'-10 C. Upon completion of the couplingreaction, the dye compound formed is salted out by the addition ofsodium chloride and recovered by filtration. The dye compound obtainedcolors cellulose acetate silk a blue shade.

Example 9 15.4 grams of 1-amino-2-hydroxy-5-nitrobenzene are diazotizedand the diazonium compound obtained is coupled with an equivalent grammolecular weight of1-p-methoxyethyl-2,2,4-trimethyl-8-chlorotetrahydroquinoline. The dyecompound obtained colors cellulose acetate silk a -magenta shade.

Example 10 1 gram mole of 1-amino-2,4-dinitro-6-chlorobenzene arediazotized and the diazonium compound obtained is coupled with 1 grammole of 1 methyll-di-B-hydroxyethylamino -8- methyl- Coupling andrecovery of the dye compound formed may be carried out in accordancewith the general method described in Example 1. The dye compoundobtained, which has the formula:

colors cellulose acetate silk a blue shade.

Example 11 HN -0Ha O colors cellulose acetate silk reddish blue shades.

For purposes of clarity, it is here noted that the numbering of thetetrahydroquinoline nucleus employed herein is that given in Examples 6and 8, for example.

The following tabulation further illustrates the compounds includedwithin the scope of our invention together with the color they produceon cellulose acetate silk. The compounds indicated below may be preparedby diazotizing the amines listed under the heading Amine and couplingthe diazonium compoundsobtained with the compounds specified in thecolumn entitled Coupling component. The diazotization and couplingreactions may, for example, be carried out following the generalprocedure indicated in Examples 1 to 11, inclusive.

vention which are water soluble do not, of course, require the use of adispersing or solubilizing agent but may be applied to silk, wool and(depending upon the nature and position of the water-solubilizing group)organic derivatives of cellulose textile materials from an aqueoussolution of the dye which may contain salt. For a more completedescription as to how the azo dye compounds of our invention may beemployed in dyeing or coloring operations, reference may be had to ourU. S. Letters Patent No. 2,115,030, issued April 26, 1938. For a moredetailed description as to how the water soluble azo dyes of ourinvention may be employed for the coloration of Color on cellulose AmineCoupling component acetate Silk (1) 7-chlorotetrahydroquinolineYellow-orange.

(2) B-methoxytetrahydroquinoline. Do. (3)1-methyl-7-chlorotctrahydroquinolinc. Do. (4) 2, 2,i-trimethyltetrahydroquinoline. Do. (5)1-/3-hydroxyethyltctrahydroquinoline Orange. (6) 1-fi-l1ydroxyethyl-2,2, 4-trimethyltetrahydroquinoline.. Do. (7) l-hydroxypropyltetrahydroquinoline Do. (8) 1-glyceryltetrahydroquinolineDo. (9) ly-methoxy fl-hydroxypropfltetrahydroquinolinc Do. (10)l-'y-chloro-B-hydroxypropyltetrahydroquinoline. Do. (11)l-fi-sulfetoethyltetrahydroquinoline Do. (12)l-B-sullocthyltetrahydroquinoline Do. (13)1-fi-methoxyethyl-S-methyltetrahydroquino1ne. Do. (14)l-fi-hydroxypropyl-7-methyltetrahydroquinoline. Do. (l5)l-glyceryl-5-methyltetrahydroquinolinc Do.(l6)1y-hydroxypropyl-7-methyltetrahydroquinolinc D0. (1;!) l-chloro-fi-hydroxypropyl-7-methyltctrahydroquino- Do.

me. (I?) l-glyceryl-Z, 2, 4-trimethyl-7-rnethoxytetrahydroquino- Do.

me. (l9)1-glyceryl-2, 2, 4-trimethyl-5, E-dimethoxytctrahydro- Do.

quinoline. p-Nitroaniline Components l-19 above Orange to rubine.l-amino-Z-(Cl, Br, F)-4-nitrobenzene d0 Orange to violet.l-amino-ii-(Cl, Br, F)-4-nitr0benzcne .d0 olginge to ru- 1H8.l-amino-2,5-di-(Cl, Br, F)-4-nitrobenzcne .do Orange to violet.l-amino-z-hydroxy-4-nitrobenzene.-. d0 Orange-pink-runc.1-emino-2-hydroxy-1'nitro-6-(Br, Cl)-benzene d0 Orange-pink-vb 0 et.p-Aminoazobenzene Orange to red. l-emino-2,4-dinitrobenzene Red tourple. 1-amino-2, 4-dinitro4i-(Br, Cl, F)-bcnzene. Red to lue.l-nmino-Z, 4-dinitro-6-cyano-benzene l Do. 2-amino-3,5-dinitrophenylmethylsnlfone. Do. l-amino-Z, 4-dinitronaphthalene Red tobluegreen. l-ethyl-4-aminotetrahydroquinoline Rubine.2-ethyltctrahydroquinolina. Do. 4-n1eth ylaminotetrahydroquinoline Do.

It will be understood from the foregoing that the amino group which canbe present in the 3 or 4 position of the tetrahydroquinoline nucleus canbe unsubstituted or substituted. The amino group can, for example, besubstituted with an alkyl group or an acyl group such as it t I forexample. The term amino, accordingly, as used herein and in the claimsin connection with the amino group which can be present in the 3 or 4position of the tetrahydroquinoline nucleus includes the unsubstitutedamino group as well as substituted amino groups.

The azo dye compounds of our invention are, for the most part,relatively insoluble in water. Those compounds which are insoluble inwater may be advantageously employed for the direct dyeing of textilematerials by grinding the dye to a fine powder, intimately mixing itwith a suitable dispersing or solubilizing agent, and adding theresulting mixture to water or a dilute solution of soap in water to forman aqueous dyebath. Following this known preparation of the dyebath, thetextile materials to be dyed may be added to the dyebath and the dyeingoperation conducted in known fashion. The dye compounds of our intextilematerials made of or containing organic derivatives of cellulose, silkand wool or mixtures of these, reference may be had to our U. S. LettersPatent No. 2,107,898, issued February 8, 1938.

We claim: 1. The nuclear non-sulfonated azo dye compounds having thegeneral formula:

wherein R represents the residue of a benzene nucleus, B represents theresidue of a benzene nucleus, R1 represents a hydroxyalkyl alkyl group,R2 and R3 each represents a member selected from the group consisting ofhydrogen, an alkyl group and an amino group, wherein each of thehydrogen atoms shown attached to the carbon atoms numbered 2, 3 and 4can be replaced by an alkyl group and wherein the nitrogen atom numbered1 and the carbon atom numbered 4 are joined to said benzene nucleus B inpara and meta position, respectively, to the azo group shown.

lye

2. The nuclear non-sulfonated azo dye compounds having the generalformula:

wherein R represents the residue of a benzene nucleus containing a nitrogroup, B represents the residue of a benzene nucleus, R1 represents ahydroxyalkyl group, R2 and R3 each represents a member selected from thegroup consisting of hydrogen, an alkyl group and anamino group, whereineach of the hydrogen atoms shown attached to the carbon atoms numbered2, 3 and 4 can be replaced by an alkyl group and wherein the nitrogenatom numbered 1 and the carbon atom numbered 4 are joined to saidbenzene nucleus B in para and meta position, respectively, to the azogroup shown.

3. The azo dye compounds having the nuclear non-sulfonated generalformula:

wherein R and B each represents the residue of a benzene nucleus, R1represents a hydroxyalkyl group, wherein each of the hydrogen atomsattached to the carbon atoms numbered 2, 3 and 4 can be replaced by analkyl group and wherein the nitrogen atom numbered 1 and the carbon atomnumbered 4 are joined to said benzene nucleus B in para and metaposition, respectively, to the azo group shown.

4. The azo dye compounds having the general formula:

/ v /CHZOHOHCH2OH wherein X represents a member selected from the groupconsisting of hydrogen, chlorine and bromine, Y represents a memberselected from the group consisting of hydrogen and a nitro group, and Zrepresents a member selected from the group consisting of hydrogen andmethyl, said compounds being further characterized in that X and Ycannot both be hydrogen at the same time.

5. The azo dye compound having the formula:

CHzOHOHCHzOH I CH2 HzC-CH2 6. The azo dye compound having the formula:

CHzCHOHCHzOH '7. The azo dye compound having the formula:

0H zCHOHCHaOH NOVQN=N N N02 CH2 Hz CH2 8. A cellulose acetate coloredwith a nuclear non-sulfonated azo dye compound having the generalformula:

CHzCHOHCHzOH "CERTIFICATE OF comcnofl; tent No. 2,261,176.: November14., i914!) JAMES G. McNALLY, -E1"AL.

It is hereby certified that error appee rs in the printed pecificationof the above numbered patent requiring correction as follows; Page 5,fir t column, linee 2b. and 25, claim 5, for The azo dye componndshaving the nuclear non-sulfonatedread "The nuclear non-snlfonated azodye oomp oundef. having the; end that the eaid'Letters Patent should-beread with this cor-- rection therein that the same may conformto the.record of the ca se in the Patent Office.

Signed and sealed this 5rd day of March; A; D. 1914.2.

Henry Van Arsdele,

(Seal) Acting Commissioner of.Patents.

